Polyfunctional aliphatic-bis-(upsilon-triazole) compounds



United States Patent 3,161,651 POLYFUNCTIONAL ALIPHATIC-BIS-(v-TRIAZOLE) (IQMPOUNDS Harry A. Stanshury, Jr., John A. Durden, Jr., and William H. Catlette, South Charleston, W. Va, assignors g? lllnion Carbide Corporation, a corporation of New or r N0 Drawing. Filed Dec. 26, 1962, Ser. No. 247,320

- Claims. (Cl. 260-308) radicals, such that -R and -R are independently selected from the group consisting of hydrogen and the hydroxyalkyl radicals containing from 1 to about 8 carbon atoms and preferably from 1 to 4 carbon atoms, at least one of which (i.e. -R and/ or -R is a hydroXyalkyl radical; -R is an alkylene radical containing from 1 to about 8 carbon atoms and preferably from 1 to 4 carbon atoms; -R is selected from the group consisting of hydrogen, the carboXy-radical, the carbalkoxy radicals containing from 1 to about 8 carbon atoms in the alkyl moiety thereof, and a hydroxy radical sepa rated from the nearest nitrogen atom by a carbon chain of the radical R of at least 2 carbon'atoms, -R being other than hydrogen when R or R is hydrogen; -R is selected from the group consisting of the alkylene radicals containing from 2 to about 8 carbon atoms and preferably from 2 to 4 carbon atoms, and the 'oXy-bis alkylene (i.e., -alkylene-O-alkylene-), carbonyloXy-bis-alkylene (i.e., a1kylene-COO-alkylene-), and phenylene-bis-alkylene (i.e., -alkylene-C H -alkylene-) radicals containing from 1 to about 4 carbon atoms and preferably from 1 to 2 carbon atoms in each alkylene moiety thereof. Thus, the radical -R can also be designated as R R'R wherein R and -R are independently selected from the group consisting of the alkylene radicals containing from 1 to about 4 carbon wherein -R R R -R and R are defined above.

As typical of the polyfunctional organo-nitrogen corn out limiting the invention.

3,161,651 Patented Dec. 15, 1964 pounds of this invention, there can be mentioned the following:

l- Z-hydroxyethyl) -4-( l-hydroxy-l -methylethyl) -1,2,3-

triazole,

1- (Z-hydroxyethyl) -4-( l-hydroxyethyl) -1,2,3 -triazole,

1- 2-hydroxyethyl) -4,5-di l-hydroxy-l-methylethyl) 1,2,3 -triazole,

1- 2-hydroxyethyl -4-hydroXymethyl-1,2, 3 -triazole,

1- (2-hydroxypropyl -4-( l-hydroxyethyl)-1,2,3triazole,

1-carb oethoXymethylil-hydroxy-2-methylpropyl) 1,2,3-triazole,

1-carboethoXymethyl-4- l-hydroxy- 1 -methylethyl 1,2,3-triazole,

1-carboethoxymethyl-4-( l-hydroxyethyl -l ,2,3-triazole,

l-carb oethoXymethy1-4- l-hydroxymethyl) -1,2,3-

triazole,

1,5 -bis [4-( l-hydroxy-l-methylethyl)-1,2,3-triazol-1- yl] -3-oxapentane,

1,5 -bis 4,5 -di (hydroxymethyl 1,2,3-triaz0l-l-yl] -3- oxapentane,

1,5 -bis [4-hydroXymethyl-1 ,2,3 -triazol-1-yl] -3 -oxapentane,

1,5 -bis [4-( l-hydroxyethyl) 1 ,2,3 -triazol-1-yl] -3 -0Xapentane,

1,4-bis [4-hydroxymethyl-l ,2,3-triazoll-yl] butane,

1,4-bis [4-( l-hydroxyl-methylethyl) 1,2,3 -triazol-1- yl] butane,

1,4-bis [4-( l-hydroxyethyl) -1 ,2,3-triazol-l-yl] butane,

1,5 -bis [4-( l-hydroxy-l-methylethyl) -1,2,3-triazo1-1- yl] pentane,

1,5 -bis [4-( l-hydroxyethyl)1,2,3-triazol-1-y1]pentane,

1-bntyl-4,5-di( l-hydroxy-l-methylethyl) -1,2,3-triazole,

1- Z-hydroxyethyl) -4-( 1-hydroxy-2-methylpropyl) 3 1,2,3 -triazole,

1,5-bis [4-hydroXymethyl-1,2,3-triazol-1 yl]pentane,

a,a-bis [4-( l-hydroxy-l-methylethyl) -1,2,3-triazol-1- y 2- [4-( l-hydroxy-l-methylethyl)-1,2,3 -triaZol-1-yl] ethyl 4-( l-hydroxy-l-methylethyl) -1,2,3-triazo1-1-ylacetate, Y

1-carboXymethyl-4-( l-hydroxyl-methylethyl) l ,2,3-

triazole,

, 1-carboXymethyl-4-( l-hydroxyethyl) -1,2,3-triazole,

1-carbobutoXymethyl-4-hydroxymethyl-1,2,3-triazole,

I-(S-carbomethoxyoctyl) -4-hydroxymethy1-1,2,3-

triazole,

1- (4-hydroxybutyl -4- S-hydroxyoctyl) -1,2,3 -triazole,

1-( 8-hydroxyocty1) -4-(4-hydroxybutyl) -1 ,2,3-triazole,

1,2-bis [4-hydroxymethyl- 1 ,2,3-triazol-1-y1] ethane,

1,8-bis [4-hydroxymethyl1,2,3 -triazol-l-yl] octane,

1,3 -bis [4-hydroxymcthy1-1,2,3 -triazol-1-y1] -2,oXa-,

. propane,

1,9-bis [4-hydroxymethyl-1,2,3:triazol-l-yl] -5-oXa-' nonane, V

oc,oc'-bis [4-hydroxymethyl- 1,2, 3 -triazol-1-yl] -p-diethylbenzene,

4- [4-hydroXymethyl-1, 2, 3-triazol-1-yl1butyl 5- [4-hydroXymethyl-1,2,3 -triazol-1-yl] pentanoate,

and the like.

The polyfunctional organo-nitrogen compounds of this invention can be obtained by any convenient process with- A particularly suitable process in this regard, which utilizes known starting materials, involves the reaction of an acetylenic compound of the formula R1CECR2 with an azide, viz., a monoazide of the formula N R R to produce a mono-' triazole as defined above by Formula II, or a diazide 3 of the formula N -R N to produce a bis-triazole as defined above by'Formula HI.

Suitable acetylenic compounds which can be employed to produce the polyfunctional organo-nitrogen compounds of this invention include, for instance, propargyl alcohol, 2-methylbut-3-yn-2-ol, but-3-yn-2-ol, but-2-yn-l,4-diol, pent-4-yn-1-ol, hex-S-yn-l-ol, 4-metl1ylpent-1-yn-3-ol, 5- methylhex-1-yn-3-ol, oct-7-yn-1-ol, 2,5-dimethylhex-3-yn- 2,5-diol, and'the like.

Illustrative of the monoazides which can be reacted therewith are methyl azide, ethyl azide, butyl azide, octyl azide, '2-hydroxyethyl azide, 4-hydroxybutyl azide, S-hydroxy-octyl azide, 2-hydroxypropyl azide, carboxymethyl azide, Z-carboxyethyl azide, 4-carboxybutyl azide, 8- carboxyoctyl azide, 2-carboxyproyl azide, carbomethoxymethyl azide, 2-(carboethoxy)ethyl azide, Z-(carbobutoxy)ethyl azide, 4-(carboethoxy)butyl azide, 8-(carboethoxy)octyl azide, and the like.

Similarly, suitable diazides includes 1,2-bis-triazoethane, 1,4-bis-triazobutane, 1,8-bis-triazooctane, 1,3-bistriazo-Z-oxapropahe, 1,5-bis-triazo-3-oxap'entane, 1,9-bistriazo-S-oxanonane, a,a-bis-triazo-p-diethylbenze-ne, 2- triazoethyl 2 triazoacetate, 4-triazobutyl 5-triazopentanoate, and the like.

The reaction producing the polyfunctional organo-nitrogen compounds of this invention can be carried out by bringing theacetylenic compound into admixture with the azide in an inert organic solvent. The resulting mixture is then heated, preferably under refiux, at a temperature of from about 30 C. up to the reflux temperature of the solvent, and preferably at a temperature of from about 60" C. to about 100 0., depending for the most part upon the particular solvent employed. Suitable solvents for use in this connection include, for instance toluene, benzene, heptane, acetone, ethanol, butanol, and the like.

The proportion in which the reactants are employed can vary broadly, with optimum results, measurable in terms of highest yields, being obtained when the reactants are employed in an approximately stoichiometric proportion. The amount of solvent present need only be sulficient to dissolve the reactants and provide a homogeneous reaction mixture, although an excess of solvent is generally employed.

The reaction period can also vary broadly, and need only'be suflicient to produce the desired product. Thus, the reaction period can vary from as little as about 1 hour up to several days or more, if desired. The polyfunctional organo-nitrogen compound thereby formed can subsequently be recovered in any convenient manner. For instance, the solvent present can be removed by dis- Table tillation or evaporation and the product thereafter purified by crystallization or further distillation. Alternatively if the product is neither crystalline nor stable at its boiling point, the product can be used in the many applications described below as the residue product obtained upon removal of the solvent and any unreacted material present.

It is to be noted that, when an asymmetrical acetylenic compound is employed as a reactant, the polyfunctional 'organo-nitrogen product may constitute an isomeric mixture of compounds in which the substituents R and R as defined above in connection with Formulas I to III are interchanged, with the isomer-of greatest bulk in the 4-position generally predominating. Such isomeric mixture can be resolved, if desired, or utilized as such in the applications described below. For convenience, however, only one such isomer is mentioned for each of polyfunctional organo-nitrogen compounds specifically disclosed herein.

The production of the polyfunctional organo-m'trogen compounds of this invention can be illustrated by the following examples.

EXAMPLE I A mixture of 14 grams (0.25 mole) of propargyl alcohol and 32 grams (0.25 mole) of carboethoxymethyl azide, disolved in milliliters of ethanol, was heated at reflux for a period of about four days. The reaction mixture was then concentrated on a rotary evaporator at room temperature under a reduced pressure of l-Z mm. of Hg to remove the solvent and any unreacted material present. In this manner, an essentially quantitative conversion to l-carboethoxymethyl-4-hydroxymethyl-l,2,3- triazole, the residue product, was obtained.

EXAMPLES II TO XVIII In the following examples, the results of which are tabulated below in Table A and B, various other organo-nitrogen compounds of this invention were produced. In each instance, the reactants were brought into admixture in a stoichiometric proportion, dissolved in the solvent indicated, and heated at the temperature and for theperi- 0d of time indicated in a manner similar to that described above in Example I. The organo-nitrogen product was thereafter recovered by distillation when a boiling point range is tabulated, by crystallization when a melting point range is given, or as a residue product upon removal of solvent and any unreacted material present. In Table A, the product obtained and the reactants employed in each of the examples are described, while in Table B, the reaction conditions and product analyses are set forth.

Organomitrogen Product Acetylenic Reactant Azide Reactant 1,4-Bis[4-hydroxymethyl-1,2,3-triaz0l-1-yl]butane 1,4-Bis[4-(l-hydroxy-l-methylethyl)-1,2,3-triazol-1-y1] ne. 1,5-Bis[4-(l-hydroxy-l-methylethyl)-1,2-3-triazol-ly11pentane. 1,5-B is[4-(1-hydroxyethyl) -1,2,3-triazol-1-yl1pentane. l-(z-Hydroxyethyl)-4-(l-hydroxy-2-methylpropyl)- 1,2,3-triazole. a,a"-Bis[4-(l-hydroxy-l-methylethyl) 1,2,3-triaz0l-lyl]-pxylene. 2-[4-(l-hydroxy-l-methylethyl)-l,2,3-triazol-l-yl]ethyl 4-(1-hydroxy-1-methylethyl)-1,2,3-triazol-1-yl-acetate 1-Butyl-4,5-di(l-hydroxy-l-methylethyl)-1,2,3-triazole.

Propargyl alcohol 1,4-Bis-triazobutane. 2-Methylbut-3-yn-2-ol.-- 1,4-Bis-triazobutane.

But-1-yn-3-ol 1,5-Bis-triazo-3-oxapentane.

2-Methylbut-3-yn-2-ol Oarboethoxymethyl azide.

2,5-Dimethylhex-3-yn-2,5-diol 2-Hydroxyethyl azide.

2-Methylbut-3-yn-2-ol Z-Hydroxyethylazide.

Propargyl alcohol Z-Hydroxyethyl azide. But-3-yn-2-ol 2-Hydroxypropyl azide. Proparg'yl alcohol Carboethoxyrnethyl azide.

2-Methylbut-3-yu-2ol But-2-yn-l,4-dio1 Propargyl alcohol.--

2-Methylbut-3-yn-2-ol Bub-3-yn-2-ol 4Methyl-pent-l-yn-3-ol .1

2-Methylbut-3-yn-2-ol Z-Methylbut-B-yn-Z-ol 2,5-Dimethylhex-3-yn-2,5-diol 1,5-Bis-triazo-3-oxapentane.

1,5-Bis-triazo-3-oxapentane.

1,5-Bis-trlazo-3-oxapentano.

1,5-Bis-triazopentane.

1,5-l3is-triazopentane. 2-Hydroxyethyl azlde.

2-Triazoethyl, 2-tri-azoacetatc.

Butyl azide.

stock formulation with water.

Table B Reaction Reaction Carbon Hydrogen Nitrogen Example Reaction Temperature Time Yield B.P. C./mm. Solvent 0.) (Hrs.) Hg) M.P C.)

Cale. Found Gale. Found Cale. Found II Toluene Steam Bath--- 24 71 47.6 47. 5 6. 4 6. 4 33.3 33.0 III dn rlo 24 48 54. 5 54.1 7.8 7. 7 27.3 27.2 IV Toluene and Reflux 143 20 48.6 48.2 6.8 6.8 28. 4 28.2

24 80 56.9 56. 7 7. 7 7. 4 16. 6 16. 6 21 52.4 52.8 8.4 8.2 18. 3 18. 5 16 20 49. 1 49.3 7. 7 7. 6 24. 6 24. 2 3. 6 96 42.0 41. 9 6. 3 6. 3 29. 4 29. 4 48 69 49. 1 49. 2 7. 7 7. 7 24. 6 24. 8 18 85 45. 4 45. 4 6.0 6. 22. 7 22. 9 23 93 57. 8 49.9 7. 7. 2 27.8 26.0 20-22 37 43.8 43.8 6.1 6.1 25. 6 25. 4 24 86 44.8 44. 5 6.0 6. 0 31.3 31.2 24 93 55. 9 54. 5 8.1 8.0 26. 1 26.7 24 82 53.0 58.0 7. 5 7. 7 28. 6 32. 2 72 55 49.6 49. 6 6. 8 7. 1 31.6 31.1 XVII d0 Reflux 24 42 60. 7 60. 6 6. 8 7.0 23. 6 23. 7 Steam Bath. 24 65 49.6 48. 4 6. 6 6.6 24.8 25. 8 Reflux 24 73 59. 7 60. 1 9. 6 9. 6 17. 4 17. 7

The organo-nitrogen compounds of this invention are useful in pesticidal applications, particularly as fungi be tested in 50 milliliters of acetone in which there was also dissolved 0.1 gram (10 percent by weight of the organo-nitrogen compound) of Triton X-155, an alkylphenoxy polyethoxyethanol surfactant, as an emulsifying or dispersing agent. The resulting solution was mixed into 200 milliliters of water to give roughly 250 milliliters of a suspension containing the compound in finely divided form. The thus-prepared stock suspension contained 0.4 percent by weight of compound. The test concentrations employed in the tests described hereinbelow were obtained by diluting the stock suspension with water.

The tests employed were as follows:

EARLY BLIGHT FUNGICIDE TEST For each test compound, a standard tomato plant, variety Bonny Best, was sprayed while revolving on a turntable with 100110 milliliters of a water solution containing 100 parts of the test compound per million parts of solution, obtained by diluting the above-described Application was made by means of a DeVilbiss spray gun set at 40 p.s.i.g. and lasted thirty seconds. After the spray had dried, the

plants were inoculated with the causitive fungus of theearly blight disease, viz. Alternaria solani, by placing the potted plants on a revolving turntable and spraying the plants with a spore suspension of the organism containing 25,000 to 30,000 spores per milliliter. Spraying Was carried out by means of a DeVilbiss spray gun set at p.s.i.g. and lasted 30 seconds. (The fungi used in inoculation had been reared on potato dextrose agar in Petri dishes at 20 C. and were transferred 10 days prior to use and scraped and irradiated with ultraviolet light seven days after transfer.) The inoculated plants were incubated for twenty-four hours at 72 F. and 100 percent relative humidity and then held for an additional twentyfour hour period at room temperature. After this holding period, results were observed by counting the total number of lesions on one magnification field (15 X) for each of eleven leaflets growing near the three top leaves of each plant. A similar count was made on control plants treated as described above but without addition of test compound. The number of lesions on treated and untreated plants were then compared and each test com- .compound, were also sprayed on infested plants.

pound was rated by calculating percent control, defined as No. of lesions on untreated plant-No. of lesions on treated plant No. of lesions of untreated plant MITICIDE TEST Adults and nymph stages of the two-spotted mite (T etranychus telarium L.), reared on Tendergreen bean 7 plants at 801- F. and 50:5 percent relative humidity,

suspension containing 2500 parts of test compound per million parts of final formulation. The potted plants (one pot per compound) were placed on a revolving turntable and sprayed with 100-110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at 40 p.s.i.g. air pressure. This application, which lasted 30 seconds, was sufficient to wet the plants to run-oil. As a control, 100110 milliliters of a water solution containing acetone and emulsifier in the same concentrations as the test compound formulation, but containing no test The sprayed plants were held at 80i5 F. and 50:5 percent relative humidity for four days, after which a mortality v count of motile forms was made on the leaves of the test plants. Any individual which was capable of locomotion upon prodding was considered living.

NEMATOCIDE TEST Infective migratory larvae of the root-knot nematode (Meloidogyne incognita, var. acrila), reared in the greenhouse on roots of Rutgers variety tomato plants constituted the test organism. Infected tomato plants were removed from the culture and the roots Were chopped very finely. A small amount of these choppings was added to a pint Mason jar containing approximately cubic centimeters of composed loam soil. The jar was capped and incubated for one week at room temperature. During the incubation period, eggs of the nematode hatch and the larval forms migrate into the soil. The treating solution of the test compound was formulated by diluting the stock suspension with water to give a suspension containing 2000 parts of test compound per million parts of final formulation. Twenty-five milliliters of the treating solution were added to each of two jars. Thus, each jar contained 50 milligrams of test compound, an amount' roughly equivalent to 375 pounds per acre. the introduction of the treating solution, the jars were capped andthe contents thoroughly mixed on a ball mill for five minutes. The jars remained capped at room temperature for 48 hours whereupon the contents were transferred to 3-inch pots. Thesepots were then seeded with melon or cucumber as an indicator crop and placed in the greenhouse where they were cared for in the usual fashion for approximately three weeks. The melon or cucumber plants were removed from the pots and the soil was washed from the roots. The amount of galling was determined by visual inspection and rated.

FLY REPELLENCY TEST Four to six day old adult houseflies (Musca domestica, L.) reared according to the specifications of the Chemical Specialties Manufacturing Association [Blue Book (Mac- Nair-Dorland Co., New York) pp. 243-44 and 261, 1954] under controlled conditions of 80:5 percent relative humidity, were the'test insects. The adult'flieswere immobilized by anesthetizing with carbon dioxide and 25 insects (males and females) were then transferred to a cage consisting of astandard food strainer five inches in diameter inverted over a six inch by six inch blotting paper. The treating'solution of the test compound was formed by dissolving the compound in acetone to give a solution containing 2.5 weight percent of compound. For each compound, two strips of one inch by two inch White blotting paper, containing three small punched holes, were treated by dipping in the solution of the test compound, allowed to dry for 24 hours, and then backed with a piece of adhesive tape over the holes. A drop of Diamalt extract was placed in each of the three holes punched in the strips. About one :hour following recovery from the anesthetic, the flies were allowed to feed on untreated bait strips introduced into the cage for a period of three minutes and the'number'of flies feeding or resting on the untreated stripswere-counted. After the three-minute period, treated strips were substituted for the untreated strips. After 15 minutes a count was made of the number offliesfeeding or resting on the treated strips. The tests were carried out atSOiS" F. and 501-5 percent relative humidity.

The results were calculated using the following equation:

T X 100 Percent repellenc y where A=number feeding on untreated strip. B=nurnber feeding on treated strip.

The results of the above-described tests are set forth in Table C, below. In the table, the ratings are based upon comparison of the effectiveness of the test compound with a control in which no test compound was employed, and vary over arange of from .0 for the con- Following H trol to 5. For instance, a rating of 1 indicates poor effectiveness, a rating of 3 indicates fair to good effectiveness, while a rating of 5 indicates excellent effectiveness. Where no rating is given, the particular test was not carried out.

Table C Organo-nitrogen Early Mitieide Nemato Fly Repel- Oompound (Ex- Blight Rating cidc Rating lency ample) Rating Rating wherein R and R are independently selected from the, group consisting of hydrogen and hydroxyalkyl of from 1 to 8 carbon atoms, at least oneof which is hydroxyalkyl; and R is selected from the group consisting of alkylene of from 2 to '8 carbon atoms and oxy-bis-alkylene, carbonyloxy-bis-alkylene, and phenylene-bis-alkylene of from 1 to 4 carbon atoms in each alkylene moiety thereof.

2. l,4-'bis [4-hydroxymcthyl-1,2,3-triazol-1-yl]butane.

3. 1,5'-bis[4-(l -'hydroxyethyl) 1,2,3 triazol-1-yl]-3- oxapentane.

4. a,a'-bis[4-(1-hydroxy 1 methylethyl) -1,2,3-triazol- 1 -yl] -p-xylene.

5. 2-[4-(1'-hydroxy 1 methylethyl) 1,2,3-triazol-1- yl] -ethyl 4-( l-hydroxyl-methylethyl) -1,2,3-triazol-1-ylacetate.

OTHER REFERENCES Moulin: Chem. Abstracts, vol. 46, pages 8651-2 (1952). 

1. THE ORGANO-NITROGEN COMPOUND OF THE FORMULA: 